Direct Amination of Arenes with Azodicarboxylates Catalyzed by Bisulfate Salt/HFIP Association

Abstract

A mild and efficient amination of arenes with azodicarboxylates using potassium bisulfate (KHSO 4 ) as the catalyst in 1,1,1,3,3,3-hexafluoro-2-propanol has been developed. This protocol allowed the amination of a broad range of arenes leading to corresponding hydrazides in good to excellent yields.

“Haliranium Ion”‐Induced Intermolecular Friedel‐Crafts Alkylation in HFIP: Synthesis of β,β‐Diaryl α‐Halo carbonyl Compounds

“…[30] It has been proven that HFIP activates the carbonyl group (C=O) of the various carbonyl compounds by establishing the hydrogen-bond-network. In general, several most reactive carbonyl compounds such as acid chloride (Friedel-Crafts acylation and thioesterification), [20] azadicarboxylate (arene amination), [31] o-aminobenzaldehyde derivatives (Tert-amino effect/1,5-H-transfer reaction), [32] N-halosuccinimide (arene halogenation, [33] polyene-cyclization [11] ), and other carbonyl substrates [34] have been successfully employed. The significant role of HFIP in these reactions has also been demonstrated by taking into account the results of Nuclear Magnetic Resonance (NMR)-experiments.…”

Aerobically-initiated C(sp3)–H bond amination through the use of activated azodicarboxylates

“…This finding not only informs the reactions disclosed in this article but also a number of recent reports in the literature that utilise this combination. [47][48][49][50] We also anticipate that the interaction we detail between fluorinated alcohols and azodicarboxylates will provide new opportunities for X-N bond formations, particularly in radical-based synthesis. Moreover, the formed ether-azodicarboxylate adducts offer opportunity for further synthetic manipulation, and in particular, to gain access to α-amino ethers.…”

AgF‐Mediated Electrophilic Amination of Alkoxyarylsilanes with Azodicarboxylates

“…Other chemicals were obtained from commercial sources and used as received unless otherwise noted. Among the products, 3 a , 3 b , 3 f , 3 k , 3 m , 3 p , 3 q , 3 r , 4 a , 5 a are known compounds, [13b,19–23] the other compounds, 3 c , 3 e , 3 g , 3 h , 3 i , 3 j , 3 l , 3 n are new compounds and were fully characterized.…”